Combined visible and near-infrared OPA for wavelength scaling experiments in strong-field physics

We report the operation of an optical parametric amplifier (OPA) capable of producing gigawatt peak-power laser pulses with tunable wavelength in either the visible or near-infrared spectrum. The OPA has two distinct operation modes (i) generation of >350 uJ, sub 100 fs pulses, tunable between 1250 - 1550 nm; (ii) generation of >190 uJ, sub 150 fs pulses tunable between 490 - 530 nm. We have recorded high-order harmonic spectra over a wide range of driving wavelengths. This flexible source of femtosecond pulses presents a useful tool for exploring the wavelength-dependence of strong-field phenomena, in both the multi-photon and tunnel ionization regimes.Comment: 14 pages, 9 figures, This paper was published in Proceedings of SPIE 10088, Nonlinear Frequency Generation and Conversion: Materials and Devices XVI, doi 10.1117/12.225077

Time-resolved optical studies, heat dissipation and melting of Ag and Au nanoparticle systems and arrays

Transient absorption spectroscopy has been extensively used in recent years to examine the temporal response of isolated nanoparticles (NPs) to the absorption of light [1]. These studies are largely based on the use of the surface plasmon resonance (SPR) to monitor characteristics of the NP such as electronic and lattice temperature, shape and morphology as a function of time. In the case of extended Au/Ag NP structures the plasmon resonance is strongly distorted due to the inter-particle coupling effects. For example, we have observed this effect in Rhodamine dye functionalized Au nanoparticles which undergo self-assembly to form nanostructures due to the interactions between the dye molecules attached to the surfaces of the nanoparticles. Indeed the SPR splits into two with one resonance remaining in the vicinity of that of the isolated AuNPs and is generally called the transverse SPR while a second resonance due to an extended excitation spanning across multiple particles appears to the lower energies. The precise spectral energy and shape of the extended plasmon resonance depends on the inter-particle distance, the particle disposition and the number of particles involved. When the plasmon band or interband spectral region of the NP is excited by an intense pulse the photon energy absorbed by the electrons is transferred to the lattice of the NP as heat through electron-phonon coupling. Depending on the intensity of the light pulse and thus the initial electron temperature a number of outcomes are possible. The first aim of this work is to use low intensity pump pulses to study the wavelength dependence of the sub 10 ps dynamics which reflects the electron-photon scattering within the nanoparticle structure. On the other hand, the interaction of more intense light with the NPs can modify the morphology of NP systems, for example by reshaping gold nanorods into nanospheres or, in general, mediate the synthesis of metallic nanostructures. At medium intensities the initial temperature is sufficient to induce melting of the NPs which can lead to morphological changes of the NP structure. Higher intensities can cause other effects such as photofragmentation of the NPs, release of stabiliser molecules from the surface of the NPs or even Coulomb explosion due to multiple ionisation events. The second aim of this work is to concentrate on the effects of medium intensity laser excitation of a self-assembled Au/Ag NP systems. The NP system is excited by a femtosecond laser pulse of different wavelengths allowing selective deposition of energy and the subsequent heat dissipation through phonon-phonon coupling and morphological changes are monitored in time by recording transient absorption spectra in the visible range. This wavelength range makes it possible to follow the phonon-phonon coupling effects on the recovery of the bleaching of both the transverse and extended plasmon resonances of the NP system. As the intensity of the pump pulse is increased it can be seen that the NPs are no longer able to dissipate all of the heat before arrival of subsequent laser pulses thus leading to melting of the NP structure and strong changes in the plasmon response of the system. The overall aim of this study is to fully understand the delocalized electron-phonon coupling in the extended plasmon region of the NP structures and to use this knowledge to control the melting in nanostructures. The methods developed can be useful for plasmon mediated nano-engineerin

Ultrafast Charge Carrier Dynamics in Vanadium-Modified TiO2 Thin Films and Its Relation to Their Photoelectrocatalytic Efficiency for Water Splitting

Light absorption and charge transport in oxide semiconductors can be tuned by the introduction, during deposition, of a small quantity of foreign elements, leading to the improvement of the photoelectrocatalytic performance. In this work, both unmodified and vanadium-modified TiO2 thin films deposited by radio-frequency magnetron sputtering are investigated as photoanodes for photoelectrochemical water splitting. Following a structural characterization by X-ray diffraction, atomic force microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy, photoelectrocatalysis is discussed based on ultrafast transient absorbance spectroscopy measurements. In particular, three different pump wavelengths from UV to the visible range are used (300, 390, and 530 nm) in order to cover the relevant photoactive spectral range of modified TiO2. Incident photon-to-current conversion efficiency spectra show that incorporation of vanadium in TiO2 extends water splitting in the visible range up to approximate to 530 nm, a significant improvement compared to unmodified TiO2 that is active only in the UV range less than or similar to 390 nm. However, transient absorbance spectroscopy clearly reveals that vanadium accelerates electron-hole recombination upon UV irradiation, resulting in a lower photon-to-current conversion efficiency in the UV spectral range with respect to unmodified TiO2. The new photoelectrocatalytic activity in the visible range is attributed to a V-induced introduction of intragap levels at approximate to 2.2 eV below the bottom of the conduction band. This is confirmed by long-living transient signals due to electrons photoexcited into the conduction band after visible light (530 nm) pulses. The remaining holes migrate to the semiconductor-electrolyte interface where they are captured by long-lived traps and eventually promote water oxidation under visible light

Environmental variables affecting an arid coastal nebkha

Foredunes in arid coastal dune systems comprise nebkhas, which originate by interactions between vegetation and aeolian sedimentation. While continuous foredunes in temperate climates have been widely studied, knowledge of interactions between biotic and abiotic drivers in foredunes formed by nebkha is still scarce. With the aim of exploring variables affecting arid foredunes, a range of morphological, sedimentological, and vegetation characteristics were measured on a single nebkha formed by a Traganum moquinii plant located in the foredune of Caleta de Famara beach (Lanzarote, Canary Islands). Variables were sampled at 120 plots in a 0.5 × 0.5 m square grid. A two-step process using multiple linear regression (MLR) analyses was developed to characterize 1) the influence that morphological variables and distance from the sea have on plant and sediment patterns on nebkha, and 2) the influence of plants on depositional sediment characteristics. Results indicate close relationships between distance from the sea, plant coverage, and sediment patterns. Empirical results were used to develop a conceptual model that explains the spatial distribution of bio- and geo-morphological characteristics of an arid nebkha foredune.Spanish Ministry of Economy, Industry and Competitiveness contract (BES-2017-082733

A study of the norcaradiene-cycloheptatriene equilibrium in a series of azulenones by NMR spectroscopy; the impact of substitution on the position of equilibrium

A systematic investigation of the influence of substitution at positions C-2 and C-3 on the azulenone skeleton, based on NMR characterisation, is discussed with particular focus on the impact of the steric and electronic characteristics of substituents on the position of the norcaradiene-cycloheptatriene (NCD-CHT) equilibrium. Variable temperature (VT) NMR studies, undertaken to enable the resolution of signals for the equilibrating valence tautomers revealed, in addition, interesting shifts in the equilibrium

Emissions and topographic effects on column CO_2 (XCO_2) variations, with a focus on the Southern California Megacity

Within the California South Coast Air Basin (SoCAB), X_(CO)_2 varies significantly due to atmospheric dynamics and the nonuniform distribution of sources. X_(CO)_2 measurements within the basin have seasonal variation compared to the “background” due primarily to dynamics, or the origins of air masses coming into the basin. We observe basin-background differences that are in close agreement for three observing systems: Total Carbon Column Observing Network (TCCON) 2.3 ± 1.2 ppm, Orbiting Carbon Observatory-2 (OCO-2) 2.4 ± 1.5 ppm, and Greenhouse gases Observing Satellite 2.4 ± 1.6 ppm (errors are 1σ). We further observe persistent significant differences (∼0.9 ppm) in X_(CO)_2 between two TCCON sites located only 9 km apart within the SoCAB. We estimate that 20% (±1σ confidence interval (CI): 0%, 58%) of the variance is explained by a difference in elevation using a full physics and emissions model and 36% (±1σ CI: 10%, 101%) using a simple, fixed mixed layer model. This effect arises in the presence of a sharp gradient in any species (here we focus on CO_2) between the mixed layer (ML) and free troposphere. Column differences between nearby locations arise when the change in elevation is greater than the change in ML height. This affects the fraction of atmosphere that is in the ML above each site. We show that such topographic effects produce significant variation in X_(CO)_2 across the SoCAB as well

A Fast Transient Absorption Study of Co(AcAc)3

The study of transition metal coordination complexes has played a key role in establishing quantum chemistry concepts such as that of ligand field theory. Furthermore, the study of the dynamics of their excited states is of primary importance in determining the de-excitation path of electrons to tailor the electronic properties required for important technological applications. This work focuses on femtosecond transient absorption spectroscopy of Cobalt tris(acetylacetonate) (Co(AcAc)3) in solution. The fast transient absorption spectroscopy has been employed to study the excited state dynamics after optical excitation. Density functional theory coupled with the polarizable continuum model has been used to characterize the geometries and the electronic states of the solvated ion. The excited states have been calculated using the time dependent density functional theory formalism. The time resolved dynamics of the ligand to metal charge transfer excitation revealed a biphasic behavior with an ultrafast rise time of 0.07 ± 0.04 ps and a decay time of 1.5 ± 0.3 ps, while the ligand field excitations dynamics is characterized by a rise time of 0.07 ± 0.04 ps and a decay time of 1.8 ± 0.3 ps. Time dependent density functional theory calculations of the spin-orbit coupling suggest that the ultrafast rise time can be related to the intersystem crossing from the originally photoexcited state. The picosecond decay is faster than that of similar cobalt coordination complexes and is mainly assigned to internal conversion within the triplet state manifold. The lack of detectable long living states (>5 ps) suggests that non-radiative decay plays an important role in the dynamics of these molecules

The role of the partner atom and resonant excitation energy in ICD in rare gas dimers

We show experimental evidence for Interatomic Coulombic Decay (ICD) in mixed rare gas dimers following resonant Auger decay. A velocity map imaging apparatus together with a cooled supersonic beam containing Ar2, ArNe and ArKr dimers was used to record electron VMI images in coincidence with two mass selected ions following excitation on five resonances converging to the Ar+ 2p−11/2 and 2p−13/2 thresholds using the synchrotron radiation. The results show that the kinetic energy distribution of the ICD electrons observed in coincidence with the ions from Coulomb explosion of the dimers depends on the partner ion and resonant photon energy